Structure-property relationships in renewable composites of poly(lactic acid) reinforced by low amounts of micro- and nano-kraft-lignin.

We investigate the direct and indirect effects of micro- and nano-kraft lignin, kL and NkL, respectively, at a quite low amount of 0.5 wt%, in poly(lactic acid) (PLA)-based composites. These renewable composites were prepared via two routes, either simple melt compounding or in situ reactive extrusion. The materials are selected and prepared using targeted methods in order to vary two variables, i.e., the size of kL and the synthetic method, while maintaining constant polymer chain lengths, L-/D-lactide isomer ratio and filler amounts. The direct/indirect effects were respectively investigated in the amorphous/semicrystalline state, as crystallinity plays in general a dominant role in polymers. The investigation involves structural, thermal and molecular mobility aspects. Non-extensive polymer-lignin interactions were recorded here, whereas the presence of the fillers led to both enhancements and suppressions of properties, e.g., glass transition, crystallization, melting temperatures, etc. The local and segmental molecular dynamics map of the said systems was constructed and is shown here for the first time, demonstrating both expected and unexpected trends. An interesting discrepancy between the trends in the calorimetric measurement against the dielectric Tg is revealed, providing indications for 'dynamical heterogeneities' in the composites as compared to neat PLA. The reactive extrusion as compared to compounding-based systems was found to exhibit stronger effects on crystallizability and mobility, most, probably due to the severe enhancement of the chains' diffusion. In general, the effects are more pronounced when employing nano-lignin compared to micro-lignin, which is the expected beneficial behaviour of nanocomposites vs. conventional composites. Interestingly, the variety of these effects can be easily manipulated by the proper selection of the preparation method and/or the thermal treatment under relatively mild conditions. The latter capability is actually desirable for processing and targeted applications and is proved here, once again, as an advantage of biobased polyesters such as PLA.

Hydration effects on thermal transitions and molecular mobility in Xanthan gum polysaccharides.

In this work, the xanthan gum (XG) polysaccharide is studied over a wide range of temperatures and water fractions 0 ≤ hw ≤ 0.70 (on a wet basis) by employing differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS). The investigation reveals that the critical water fraction for ice formation is about 0.35. Glass transition temperature (Tg) was determined through calorimetry experiments for all the samples studied. Water acts as a strong plasticizer, i.e., decreasing Tg, for water fractions up to about 0.35. A secondary (local) relaxation process is recorded in both dry and hydrated samples, which is sensitive to the presence of water molecules. This fact indicates that this process originates due to the orientation of small polar groups of the side chain, or/and due to the local main chain dynamics. Two types of long-range charge transport processes were resolved. The first is related to the conductive paths being formed via bulk-like ice structures (at high hydration levels), whereas the second can be attributed to proton mobility via the hydrogen bond (HB) network of non-freezing water existing in XG. Interestingly, this process is exactly the same in all the hydrated samples with hw > 0.25. With respect to the sample with hw = 0.27, a Vogel-Tammann-Fulcher (VTF)-like polarization process has also been recorded which seems to be related to long-range charge mobility via interconnected water clusters. As far as we are aware, this is the first time that XG is studied in terms of glass transition and molecular mobility over a wide range of hydration levels combining DSC and BDS techniques.

Segmental mobility in sustainable copolymers based on poly(lactic acid) blocks built onto poly(butylene succinate) in situ.

Two series of newly synthesized sustainable block copolymers based on poly(butylene succinate) (PBSu) and polylactide (PLA) were studied. The copolymers were synthesized by a ring-opening polymerization of PLA in the presence of two initial PBSu of low molar mass. We focused on the effects of the PBSu/PLA ratio (1/99 up to 15/85), chain length and initial PBSu length on the final thermal transitions in the copolymers with an emphasis on molecular mobility/dynamics and subsequently on crystallization. Both aspects are considered relevant to the final materials performance, as well as facilitation of polymer renewability. Calorimetry and dielectric spectroscopy were the main investigation tools. In the amorphous state (i.e., in which the direct effects of copolymer structure are assessable), the segmental mobility of neat PLA was significantly faster in the copolymers. Segmental mobility was monitored via the decrease in the calorimetric and dielectric (α relaxation) glass-transition temperatures, Tg and Tg,diel, respectively. The effect was systematic with an increase in the PBSu/PLA ratio, and was rationalized through the plasticizing role of PBSu (low-Tg component) and facilitated also by the simultaneous lowering of the chain length in the copolymers. Dielectric spectroscopy allowed evaluation of the dynamical fragility (cooperativity) of chains, which was strongly suppressed in the copolymers. This finding suggested an increase in free volume or a gradual increase of interchain distances. This phenomenon could favor the natural enzymatic degradation of the systems (compostability), which is limited in neat PLA. We recorded enhancement of nucleation and the crystalline fraction in the copolymers that was likely connected with faster chain diffusion. Further lowering of the Tg with the implementation of crystallization was noted (which seemed a controversial effect) but which indicated crystallization-induced phase separation.

Effects of Segment Length and Crosslinking via POSS on the Calorimetric and Dynamic Glass Transition of Polyurethanes with Aliphatic Hard Segments.

The glass transition in polyurethanes is a complicated phenomenon governed by a multitude of factors, including the microphase separation, which in turn depends strongly on the molar mass of the hard and soft segments, as well as the presence of additives. In this work, we study the effects of the segments' length on the microphase separation and consequently on the calorimetric and dynamic glass transition of a polyurethane with aliphatic, "flexible" hard segments. It is found that the dependence of the calorimetric glass transition follows the same principles as those in systems with aromatic hard segments. Strikingly, however, the dynamic glass transition, as studied by dielectric spectroscopy, shows a slowing down of its dynamics despite a decrease in Tg. This discrepancy is discussed in terms of the strong dielectric response of the flexible segments, especially those close to the interface between the hard domains and soft phase, as opposed to a weak thermal one. In addition, polyhedral oligomeric silsesquioxanes (POSS) are introduced in the soft phase of the three matrices as crosslinking centres. This modification has no visible effect on the calorimetric glass transition; nevertheless, it affects the microphase separation and the dielectric response in a non-monotonic manner.

Crystallization and molecular mobility in renewable semicrystalline copolymers based on polycaprolactone and polyisosorbide.

A series of novel block copolymers based on two biodegradable polymers, poly(ε-caprolactone), PCL, and poly(isosorbide), PIS, with PIS fractions 5, 10, and 25 wt%, are studied herein. The aim is to assess the effects of the amorphous PIS phase on the properties of the semicrystalline PCL (majority), in addition to the synthesis strategy. The latter involved the polymerization of caprolactone onto initial PIS of low molar mass, resulting, thus, in gradually shorter PCL blocks when the starting amount of PIS is increased. The structure-property relationship investigation, with an emphasis on molecular mobility and crystallization, involves the following sum of complementary techniques: differential scanning calorimetry, dielectric spectroscopy, polarized optical microscopy and X-ray diffraction. The molecular mobility map for these PCL/PIS and initial PIS is drawn here for the first time. Despite the high glass transition temperature of PIS (Tg ∼ 51 °C) compared to that of PCL (-66 °C), the Tg of the copolymers barely changes, as it is mainly ruled by crystallinity. The latter seems to be facilitated in the copolymers, in both the amount and the rate. The local molecular mobility of PCL and PCL/PIS consists of faster γPCL relaxation which is unaffected in the copolymers, whereas the slower ßPCL process arising from the backbone ester group rotation exhibits a systematic deceleration in the presence of PIS. A connection between such local motions and the corresponding segmental α relaxation, observed previously in other polyesters, is also found to be true here. Apart from that, the dielectric Tg as well as the cooperativity of the polymer chains drop moderately, which indicates spatial confinement between the PCL crystals, whereas correlations with the looser lamellar chain packing within the spherulites are gained. The relaxations of initial PIS, i.e., γPIS, ßPIS and αPIS, could not be resolved within the copolymers. Along with other properties, such as ionic conductivity, we conclude to the homogeneity of our systems, with sufficient PCL/PIS distribution.

Direct and indirect effects on molecular mobility in renewable polylactide-poly(propylene adipate) block copolymers as studied via dielectric spectroscopy and calorimetry.

In this work, we study a series of sustainable block copolymers based on polylactide, PLA, and poly(propylene adipate), PPAd, both polymers being prepared from renewable resources. Envisaging a wide range of future applications in the frame of a green and circular economy, e.g., packaging materials replacing conventional petrochemicals, the employment of PPAd aims at lowering the glass transition and melting temperatures of PLA and, finally, facilitation of the enzymatic degradation and compostability. The copolymers have been synthesized via ring opening polymerization of lactides in the presence of propylene adipate oligomers (5, 15 and 25%). The direct effects on the molecular mobility by the structure/composition are assessed in the amorphous state employing broadband dielectric spectroscopy (BDS) and calorimetry. BDS allowed the recording of local PLA and PPAd dynamics in all cases. The effects on local relaxations suggest favoring of interchain interactions, both PLA-PPAd and PPAd-PPAd. Regarding the more important segmental dynamics, the presence of PPAd leads to faster polymer chain diffusion, as monitored by the significant lowering of the dielectric and calorimetric glass transition temperature, Tg. This suggests the plasticizing role of PPAd on PLA (majority) in combination with the lowering of the average molar mass, Mn, in the copolymers from ∼75 to ∼30 kg mol-1, which is the actual scope for the synthesis of these materials. Interestingly, a strong suppression in fragility (chain cooperativity) is additionally recorded. In contrast to calorimetry and due to the high resolving power of BDS, for the higher PPAd fraction, the weak segmental relaxation of PPAd was additionally recorded. Overall, the recordings suggest a strong increase in free volume and two individual dynamic states, one for 0 and 5% PPAd and another for 15 and 25% PPAd. Within the latter, we gained indications for partial phase nano-separation of PPAd. Regarding indirect effects, these were followed via crystallization. Independent of the method of crystallization, namely, melt or cold, the presence of PPAd led to the systematic lowering of crystallization and melting temperatures and enthalpies. The effects reflect the decrease of crystalline nuclei, which is confirmed by optical microscopy as in the copolymers fewer although larger crystals are formed.

Revisiting Non-Conventional Crystallinity-Induced Effects on Molecular Mobility in Sustainable Diblock Copolymers of Poly(propylene adipate) and Polylactide.

This work deals with molecular mobility in renewable block copolymers based on polylactide (PLA) and poly(propylene adipate) (PPAd). In particular, we assess non-trivial effects on the mobility arising from the implementation of crystallization. Differential scanning calorimetry, polarized light microscopy and broadband dielectric spectroscopy were employed in combination for this study. The materials were subjected to various thermal treatments aiming at the manipulation of crystallization, namely, fast and slow cooling, isothermal melt- and cold-crystallization. Subsequently, we evaluated the changes recorded in the overall thermal behavior, semicrystalline morphology and molecular mobility (segmental and local). The molecular dynamics map for neat PPAd is presented here for the first time. Unexpectedly, the glass transition temperature, Tg, in the amorphous state drops upon crystallization by 8-50 K. The drop becomes stronger with the increase in the PPAd fraction. Compared to the amorphous state, crystallization leads to significantly faster segmental dynamics with severely suppressed cooperativity. For the PLA/PPAd copolymers, the effects are systematically stronger in the cold- as compared to the melt-crystallization, whereas the opposite happens for neat PLA. The local ßPLA relaxation of PLA was, interestingly, recorded to almost vanish upon crystallization. This suggests that the corresponding molecular groups (carbonyl) are strongly involved and immobilized within the semicrystalline regions. The overall results suggest the involvement of either spatial nanoconfinement imposed on the mobile chains within the inter-crystal amorphous areas and/or a crystallization-driven effect of nanophase separation. The latter phase separation seems to be at the origins of the significant discrepancy recorded between the calorimetric and dielectric recordings on Tg in the copolymers. Once again, compared to more conventional techniques such as calorimetry, dielectric spectroscopy was proved a powerful and quite sensitive tool in recording such effects as well as in providing indirect indications for the polymer chains' topology.

High-Drug-Loading Amorphous Solid Dispersions via In Situ Thermal Cross-Linking: Unraveling the Mechanisms of Stabilization.

This article takes a step forward in understanding the mechanisms involved during the preparation and performance of cross-linked high-drug-loading (HDL) amorphous solid dispersions (ASDs). Specifically, ASDs, having 90 wt % poorly water-soluble drug indomethacin (IND), were prepared via in situ thermal cross-linking of poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA) and thoroughly evaluated in terms of physical stability and in vitro supersaturation. Results showed that HDL ASDs having excellent active pharmaceutical ingredient (API) amorphous stability and prolonged in vitro supersaturation were prepared by fine tuning the cross-linking procedure. Unraveling of the processes involved during ASD's formation shed light on the significant role of the cross-linking conditions (i.e., temperature and time), the physicochemical properties of the API, and the hydrolysis level of the cross-linker as key factors in modulating ASD's stability. In-depth analysis of the prepared systems revealed the (1) reduction of API's molecular motions within the cross-linked polymeric networks (through API's strong spatial confinement), (2) the structural changes in the prepared cross-linked matrices (induced by the high API drug loading), and (3) the tuning of the cross-linking density via utilization of low-hydrolyzed PVA as the major mechanisms responsible for ASD's exceptional performance. Complementary analysis by means of molecular dynamics simulations also highlighted the vital role of strong drug-polymer intermolecular interactions evolving among the ASD components. Overall, the impression of the complexity of in situ cross-linked ASDs has been reinforced with the excessive variation of parameters investigated in the current study, offering thus insights up to the submolecular level to lay the groundwork and foundations for the comprehensive assessment of a new emerging class of HDL amorphous API formulations.

Molecular dynamics and crystallization in polymers based on ethylene glycol methacrylates (EGMAs) with melt memory characteristics: from linear oligomers to comb-like polymers.

In this article we present results on the glass transition, crystallization and molecular dynamics in relatively novel oligomers, oligo-ethylene glycol methacrylate (OEGMA), with short and long chains, as well as in the corresponding nanostructured comb-like polymers (POEGMA, short and long), the latter being prepared via the RAFT polymerization process. For the investigation we employed conventional and temperature modulated differential scanning calorimetry in combination with high resolving power dielectric spectroscopy techniques, broadband dielectric relaxation spectroscopy (BDS) and thermally stimulated depolarization currents (TSDC). Under ambient conditions short OEGMA (475 g mol-1, ∼4 nm in length) exhibits a remarkable low glass transition temperature, Tg, of -91 °C, crystallization temperature Tc = -24 °C and a significant crystalline fraction, CF, of ∼30%. When doubling the number of monomers (OEGMA-long, 950 g mol-1, chain length ∼8 nm) the Tg increases by about 20 K and CF increases to ∼53%, whereas, the Tc migrates to a room-like temperature of 19 °C. Upon formation of comb-like POEGMA structures the grafted OEGMA short chains, strikingly, are not able to crystallize, while in POEGMA-long the crystallization behaviour changes significantly as compared to OEGMA. Our results indicate that in the comb-like architecture the chain diffusion of the amorphous fractions is also strongly affected. The semicrystalline systems exhibit significant melt memory effects, this being stronger in the comb-like architecture. It is shown that these effects are related to the inter- and intra-chain interactions of the crystallizable chains. The dielectric techniques allowed the molecular dynamics mapping of these new systems from the linear oligomers to POEGMAs for the first time. BDS and TSDC detected various dynamics processes, in particular, the local polymer dynamics (γ process) to be sensitive to the Tg, local dynamics triggered in the hydrophilic chain segments by water traces (ß), as well as the segmental dynamics (α) related to glass transition. Interestingly, both the short and long linear OEGMAs exhibit an additional relaxation process that resembles the Normal-Mode process appearing in polyethers. In the corresponding POEGMAs this process could not be resolved, this being an effect of the one-side grafted chain on the comb backbone. The revealed variations in molecular mobility and crystallization behavior suggest the potentially manipulable diffusion of small molecules throughout the polymer volume, via both the molecular architecture as well as the thermal treatment. This ability is extremely useful for these novel materials, envisaging their future applications in biomedicine (drug encapsulation).

Molecular mobility and crystallization of renewable poly(ethylene furanoate) in situ filled with carbon nanotubes and graphene nanoparticles.

We investigate the thermal transitions and molecular mobility in new nanocomposites of biobased poly(ethylene furanoate) (PEF), by calorimetry and dielectric spectroscopy, supplemented by X-ray diffraction, Fourier transform infra-red spectroscopy and polarized light microscopy. The emphasis is placed on the facilitation of the crystallization of PEF, which is in general low and slow due to structural limitations that result in poor nucleation. Tuning of the crystalline fraction (CF) and semicrystalline morphology are important for optimization of the mechanical performance and manipulation of the permeation of small molecules (e.g., in packaging applications). The nucleation and CF are successfully improved here by the in situ filling of PEF with 0.5-2.5 wt% of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs). The improvements are discussed in connection with weak or absent interfacial polymer-filler interactions. CNTs were found to be more effective in facilitating crystallization, as compared with GNPs, possibly due to their larger aspect ratio. The segmental dynamics of PEF are both accelerated and decelerated by the addition of GNP and CNT, respectively, with complex phenomena contributing to the effects, namely, nucleation, changes in molar mass and changes in the free volume. The molecular mobility of PEF is moderately affected 'directly' by the particles, whereas stronger effects are induced by crystallization (an indirect effect) and, furthermore, by the increase in the length of alkylene sequences on the chain. Local dynamics exhibit time scale disturbances when the temperature approaches that of the glass transition, which is proposed here to be a common characteristic in the case of mobilities originating from the polymer backbone for these as well as different polyesters. Despite the weak effects on molecular mobility, the role of the fillers as nucleating agents seems to be further exploitable in the frame of envisaged applications, as the use of such fillers in combination with thermal treatment offer possibilities for manipulating the semicrystalline morphology, ion transport and, subsequently, permeation of small molecules.

Block copolymers based on poly(butylene adipate) and poly(L-lactic acid) for biomedical applications: synthesis, structure and thermodynamical studies.

This work describes the synthesis of poly(butylene adipate) (PBAd), by melt polycondensation, poly(l-lactic acid) (PLLA), by ring opening polymerization, and the new block copolymer PLLA/PBAd in ratios 90/10, 95/5, 75/25 and 50/50. Due to the biocompatibility and low toxicity of neat PBAd and PLLA, these copolymers are suitable to be used in biomedical applications. The 1H and 13C nuclear magnetic resonance spectroscopy techniques were employed for structural characterization. The thermal transitions, with an emphasis on crystallization, were assessed by differential scanning calorimetry, supplemented by X-ray diffraction and polarized optical microscopy. Molecular mobility studies were conducted using two advanced techniques, broadband dielectric spectroscopy and thermally stimulated depolarization currents. The results from the structural techniques, in combination with each other, provided proof of the presence of PLLA and PBAd blocks and, moreover, the successful copolymer synthesis. The overall data showed that the different co-polymer compositions result directly in severe changes in the polymer crystal distribution and, indirectly, the formation of PBAd micro/nano domains surrounded by PLLA. Furthermore, it was demonstrated that both the continuity of the two polymers throughout the copolymer volume and the semicrystalline morphology can be tuned to a wide extent. The latter makes these systems quite promising envisaging biomedical applications, including the encapsulation of small molecules, e.g. drug solutions. The molecular mobility map was constructed for these systems for the first time, revealing the local (short scale) and segmental (larger nm scale) mobility of PBAd and PLLA, as well as intermediate behaviors of the copolymers.

Synthesis, crystallization, and molecular mobility in poly(ε-caprolactone) copolyesters of different architectures for biomedical applications studied by calorimetry and dielectric spectroscopy.

In this work, we synthesized poly(ε-caprolactone) (PCL) and three copolyesters of different architectures based on three different alcohols, namely a three arm-copolymer based on 1% glycerol (PCL_Gly), a four arm-copolymer based on 1% pentaerythrytol (PCL_PE), and a linear block copolymer based on ∼50% methoxy-poly(ethylene glycol) (PCL_mPEG), all simultaneously with the ring opening polymerization (ROP) of PCL. Due to their biocompatibility and low toxicity, these systems are envisaged for use in drug delivery and tissue engineering applications. Due to the in situ ROP during the copolyesters synthesis, the molecular weight of PCL, Wm initially ∼62 kg mol-1, drops in the copolymers from ∼60k down to ∼5k. For the structure-properties investigation we employed differential scanning calorimetry (DSC and TMDSC), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Fourier transform infra red (FTIR) spectroscopy, polarized optical microscopy (POM), broadband dielectric spectroscopy (BDS) and isothermal water sorption. DSC revealed that the crystalline fraction of PCL increases whereas the crystallization rate drops in the copolymers in the order PCL ∼ PCL_Gly > PCL_PE ≫ PCL_mPEG, which coincides with that of decreasing Wm. In PCL_mPEG the major amount of PCL (87%) was found to crystallize while the majority of mPEG (92%) was found amorphous exhibiting constrained amorphous mobility and severely slower/weaker crystallization as compared to neat mPEG. Segmental dynamics in BDS, in agreement with DSC, is similar and in general slow for the samples of star-like structure for Wm ≥ 30k arising from PCL, whereas it is severely faster and enhanced in strength for the linear PCL_mPEG (lower Wm) copolymer arising from mPEG. For the latter system, the data provide indications for the formation of complex structures consisting of many small PCL crystallites surrounded by amorphous mPEG segments with constrained dynamics and severely suppressed hydrophilicity. These effects cannot be easily assessed by conventional XRD and POM, confirming the power of the dielectric technique. The overall recordings indicated that the different polymer architecture results in severe changes in the semicrystalline morphology, which demonstrates the potential for tuning the final product performance (permeability, mechanical).

PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics.

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation α', slower than the bulky segmental α and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

Effects of CNTs on thermal transitions, thermal diffusivity and electrical conductivity in nanocomposites: comparison between an amorphous and a semicrystalline polymer matrix.

Two series of polymer nanocomposites (PNCs) based on amorphous styrene-butadiene rubber (SBR) and semicrystalline linear low-density polyethylene (PE) matrices were filled with 2-15 wt% carbon nanotubes (CNT) and were studied by employing calorimetry, dielectric spectroscopy and laser flash analysis. The electrical conductivity, σ, increased with CNT loading and similar values were exhibited for the two matrices, uniquely depending on the concentration of the CNTs, suggesting practically no effects of the crystalline fraction (CF) on σ. For both types of matrix, a fraction of the polymer was found to be immobilized (rigid amorphous fraction, RAF). For the amorphous SBR, the RAF in PNCs originates uniquely from the presence of the filler (RAFfiller up to 0.19 wt). On the other hand, for the semicrystalline PE, the RAF is significantly larger (0.4-0.6 wt) due to the severe contribution of the RAF around the crystals (RAFcrystal). The thermal diffusivity, α, is quite low in both types of PNCs and exhibits higher values in the semicrystalline matrix (PE-based PNCs). Our results suggest that in these PNCs, heat transport mechanisms are activated mainly in the crystalline domains, more so with the additive contribution of the RAFcrystal. In the amorphous SBR-based PNCs, heat transport is facilitated mainly by CNTs, whereas the RAFfiller is found to be a good measure of the thermal resistance behavior of CNT/polymer interphases and consequently, of thermal diffusivity. Direct correlation of the results obtained by the three techniques with each other revealed the systematic dependence of α on the amount of RAF in each matrix; the α(RAF) trends, however, are different for the two matrices. Furthermore, the results suggest that the two RAFs exhibit different structural characteristics, e.g. the RAFcrystal exhibits a more ordered structure than the RAFfiller; this issue is still an open debate in the literature.

Dynamics of hydration water in gelatin and hyaluronic acid hydrogels.

We employed broadband dielectric spectroscopy (BDS), for the investigation of the water dynamics in partially hydrated hyaluronic acid (HA), and gelatin (Gel), enzymatically crosslinked hydrogels, in the water fraction ranges [Formula: see text]. Our results indicate that at low hydrations ([Formula: see text]), where the dielectric response of the hydrogels is identical during cooling and heating, water plasticizes strongly the polymeric matrix and is organized in clusters giving rise to [Formula: see text]-process, secondary water relaxation and to an additional slower relaxation process. This later process has been found to be related with the dc charge conductivity and can be described in terms of the conduction current relaxation mechanism. At slightly higher hydrations, however, always below the hydration level where ice is formed during cooling, we have recorded in HA hydrogel a strong water dielectric relaxation process, [Formula: see text], which has Arrhenius-like temperature dependence and large time scale resembling relaxation processes recorded in bulk low density amorphous solid water structures. This relaxation process shows a strong-to-fragile transition at [Formula: see text]C and our data suggest that the VTF-like process recorded at [Formula: see text]C is controlled by the same molecular process like long range charge transport. In addition, our data imply that the crossover temperature is related with the onset of structural rearrangements (increase in configurational entropy) of the macromolecules. In partially crystallized hydrogels ([Formula: see text]) HA exhibits at low temperatures the ice dielectric process consistent with the bulk hexagonal ice, whereas Gel hydrogel exhibits as main low temperature process a slow relaxation process that refers to open tetrahedral structures of water similar to low density amorphous ice structures and to bulk cubic ice. Regarding the water secondary relaxation processes, we have shown that the [Formula: see text]-process and the [Formula: see text] process are activated in water hydrogen bond networks with different structures.

Applying Broadband Dielectric Spectroscopy (BDS) for the Biophysical Characterization of Mammalian Tissues under a Variety of Cellular Stresses.

The dielectric properties of biological tissues can contribute non-invasively to a better characterization and understanding of the structural properties and physiology of living organisms. The question we asked, is whether these induced changes are effected by an endogenous or exogenous cellular stress, and can they be detected non-invasively in the form of a dielectric response, e.g., an AC conductivity switch in the broadband frequency spectrum. This study constitutes the first methodological approach for the detection of environmental stress-induced damage in mammalian tissues by the means of broadband dielectric spectroscopy (BDS) at the frequencies of 1-106 Hz. Firstly, we used non-ionizing (NIR) and ionizing radiation (IR) as a typical environmental stress. Specifically, rats were exposed to either digital enhanced cordless telecommunication (DECT) radio frequency electromagnetic radiation or to γ-radiation, respectively. The other type of stress, characterized usually by high genomic instability, was the pathophysiological state of human cancer (lung and prostate). Analyzing the results of isothermal dielectric measurements provided information on the tissues' water fraction. In most cases, our methodology proved sufficient in detecting structural changes, especially in the case of IR and malignancy. Useful specific dielectric response patterns are detected and correlated with each type of stress. Our results point towards the development of a dielectric-based methodology for better understanding and, in a relatively invasive way, the biological and structural changes effected by radiation and developing lung or prostate cancer often associated with genomic instability.

Flame-Retarded and Heat-Resistant PP Compounds for Halogen-Free Low-Smoke Cable Protection Pipes (HFLS Conduits).

Conduits are plastic tubes extensively used to safeguard electrical cables, traditionally made from PVC. Recent safety guidelines seek alternatives due to PVC's emission of thick smoke and toxic gases upon fire incidents. Polypropylene (PP) is emerging as a viable alternative but requires modification with suitable halogen-free additives to attain flame retardancy (FR) while maintaining high mechanical strength and weathering resistance, especially for outdoor applications. The objective of this study was to develop two FR systems for PP: one comprising a cyclic phosphonate ester and a monomeric N-alkoxy hindered amine adjuvant achieving V0, and another with hypophosphite and bromine moieties, along with a NOR-HAS adjuvant achieving V2. FR performance along with mechanical properties, physicochemical characterization, and dielectric behavior were evaluated prior to and after 2000 h of UV weathering or heat ageing. The developed FR systems set the basis for the production of industrial-scale masterbatches, from which further optimization to minimize FR content was performed via melt mixing with PP towards industrialization of a low-cost FR formulation. Accordingly, two types of corrugated conduits (ø20 mm) were manufactured. Their performance in terms of flame propagation, impact resistance, smoke density, and accelerated UV weathering stability classified them as Halogen Free Low Smoke (HFLS) conduits; meanwhile, they meet EU conduit standards without significantly impacting conduit properties or industrial processing efficiency.

Fabrication of Poly(ethylene furanoate)/Silver and Titanium Dioxide Nanocomposites with Improved Thermal and Antimicrobial Properties.

Poly(ethylene furanoate) (PEF)-based nanocomposites were fabricated with silver (Ag) and titanium dioxide (TiO2) nanoparticles by the in-situ polymerization method. The importance of this research work is to extend the usage of PEF-based nanocomposites with improved material properties. The PEF-Ag and PEF-TiO2 nanocomposites showed a significant improvement in color concentration, as determined by the color colorimeter. Scanning electron microscopy (SEM) photographs revealed the appearance of small aggregates on the surface of nanocomposites. According to crystallinity investigations, neat PEF and nanocomposites exhibit crystalline fraction between 0-6%, whereas annealed samples showed a degree of crystallinity value above 25%. Combining the structural and molecular dynamics observations from broadband dielectric spectroscopy (BDS) measurements found strong interactions between polymer chains and nanoparticles. Contact angle results exhibited a decrease in the wetting angle of nanocomposites compared to neat PEF. Finally, antimicrobial studies have been conducted, reporting a significant rise in inhibition of over 15% for both nanocomposite films against gram-positive and gram-negative bacteria. From the overall results, the synthesized PEF-based nanocomposites with enhanced thermal and antimicrobial properties may be optimized and utilized for the secondary packaging (unintended food-contact) materials.

Synthesis of novel interpenetrated network for ocular co-administration of timolol maleate and dorzolamide hydrochloride drugs.

In the present work, novel interpenetrated networks (IPNs) of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide) (SBMA) and poly(vinyl alcohol) (PVA) were prepared for the ocular co-administration of timolol maleate (TIM) and dorzolamide hydrochloride (DORZ), two drugs widely used for the treatment of glaucoma. The successful polymerization of SBMA, in the presence of PVA, led to the formation of semi-interpenetrated pSBMA-PVA networks (IPNs), in the form of sponges, exhibiting intrinsic antimicrobial properties attributed to SBMA. Fourier-transform infrared spectroscopy (FTIR) was utilized to confirm the successful synthesis of the IPNs. Further assessments, including contact angle and water sorption measurements, highlighted their significant hydrophilicity, a feature that makes them suitable for ocular applications. Differential scanning calorimetry (DSC) measurements indicated that PVA serves as a plasticizer, while an assessment of the water sorption capacity of these materials suggested that although the incorporation of PVA results in slightly less hydrophilic materials, the prepared sponges still remain sufficiently hydrophilic for ocular use. Following their characterization, the optimal pSBMA-PVA IPN was used to encapsulate TIM and DORZ. Irritation tests, performed using the HET-CAM method, confirmed that the drug-loaded sponges were safe and potentially well-tolerated for ophthalmic use. Finally, the co-release study for the two drugs revealed a sustained release pattern in both cases, while drug release from the sponges was primarily controlled by diffusion.

Synthesis and Study of Fully Biodegradable Composites Based on Poly(butylene succinate) and Biochar.

Biodegradable polymers offer a promising alternative to the global plastic problems and especially in the last decade, to the microplastics problems. For the first time, samples of poly(butylene succinate) (PBSu) biocomposites containing 1, 2.5, and 5 wt% biochar (BC) were prepared by in situ polymerization via the two-stage melt polycondensation procedure. BC was used as a filler for the PBSu to improve its mechanical properties, thermal transitions, and biodegradability. The structure of the synthesized polymers was examined by 1H and 13C nuclear magnetic resonance (NMR) and X-Ray diffraction (XRD) along with an estimation of the molecular weights, while differential scanning calorimetry (DSC) and light flash analysis (LFA) were also employed to record the thermal transitions and evaluate the thermal conductivity, respectively. It was found that the amount of BC does not affect the molecular weight of PBSu biocomposites. The fine dispersion of BC, as well as the increase in BC content in the polymeric matrix, significantly improves the tensile and impact strengths. The DSC analysis results showed that BC facilitates the crystallization of PBSu biocomposites. Due to the latter, a mild and systematic increase in thermal diffusivity and conductivity was recorded indicating that BC is a conductive material. The molecular mobility of PBSu, local and segmental, does not change significantly in the biocomposites, whereas the BC seems to cause an increase in the overall dielectric permittivity. Finally, it was found that the enzymatic hydrolysis degradation rate of biocomposites increased with the increasing BC content.